EP0588724B1 - Feuille réceptrice d'images pour copieurs sur papier ordinaire - Google Patents

Feuille réceptrice d'images pour copieurs sur papier ordinaire Download PDF

Info

Publication number
EP0588724B1
EP0588724B1 EP19930402259 EP93402259A EP0588724B1 EP 0588724 B1 EP0588724 B1 EP 0588724B1 EP 19930402259 EP19930402259 EP 19930402259 EP 93402259 A EP93402259 A EP 93402259A EP 0588724 B1 EP0588724 B1 EP 0588724B1
Authority
EP
European Patent Office
Prior art keywords
recording sheet
acrylate
parts
meth
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19930402259
Other languages
German (de)
English (en)
Other versions
EP0588724A1 (fr
Inventor
Bill Henry C/O Minnesota Mining And Manu.Co Dodge
William Henry C/O Minnesota Min.And Man.Co Hughes
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/947,252 external-priority patent/US5310595A/en
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0588724A1 publication Critical patent/EP0588724A1/fr
Application granted granted Critical
Publication of EP0588724B1 publication Critical patent/EP0588724B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002—Organic components thereof
    • G03G7/0026—Organic components thereof being macromolecular
    • G03G7/004—Organic components thereof being macromolecular obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/254—Polymeric or resinous material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer
    • Y10T428/3192—Next to vinyl or vinylidene chloride polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31928—Ester, halide or nitrile of addition polymer

Definitions

  • the invention relates to transparencies for plain paper copiers having a transparent backing and an image-receptive coating.
  • Oriented films such as biaxially oriented poly(ethylene terephthalate) films, are widely used as a base for transparency films.
  • a thermal printer, an ink jet printer and the like such films are usually overcoated with an image-receptive layer.
  • image-receptive layers are usually coated onto the films after biaxial orientation and/or heat setting to generate a ready-to-use imaging receptor.
  • Most commercially available image receptors are made in this manner and the patent literature is full of such examples, i.e., U.S. Patent Nos. 3,539,340; 4,071,362; 4,085,245; 4,259,422 and 4,956,223.
  • Image receptors specifically useful for electrographic and xerographic copiers are also disclosed in U. S. Patent Nos. 4,480,003; 4,869,955; 4,956,225 and 5,104,731.
  • U.S. Patent No. 4,493,872 discloses a coated oriented plastic film wherein the coating is applied in an aqueous medium comprising a water dispersible copolyester during manufacture of the film, at any suitable stage, i.e., before, during, or after the stretching operations.
  • U. S. Patent Nos. 4,585,687 and 4,745,019 disclose a primer coated, oriented polyester film material wherein the primer is applied in an aqueous medium comprising a water dispersible copolyester at any suitable stage during the manufacture of the film, again either before, during or after the stretching operations.
  • Slip agents such as silicas are mentioned as additives in the coating solution.
  • Japanese Patent Publication Hei-Sei 1-160817 discloses a polyester film with antistatic properties, characterized by the fact that on at least one side of the polyester film is a thin layer comprising an acrylic-type binder resin, a copolymerized polyester resin, a microscopic particle having an average diameter of below 0.5 ⁇ m, and an antistatic agent. This coating is applied to the polyester film surface before the crystallization orientation is completely finished on the surface of the un-oriented film, or on the surface of the film that is oriented in at least one direction, in an aqueous medium.
  • the microscopic particles described can be polymeric, such as polystyrene, polymethylmethacrylate, polymethylmethacrylate copolymer material, polymethylmethacrylate copolymer material crosslinking agent, polytetrafluoroethylene, polyvinylidiene fluoride, polyacrylonitrile, benzoguanamine resin, etc., organic microscopic particle powders; silica, alumina, titanium dioxide, etc., and other inorganic particle powders.
  • the organic particle powders, especially the polymethylmethacrylate powder material is preferred.
  • the average diameter of the particles is preferably in the range of 0.01 to 0.15 ⁇ m. In the case the diameter is greater than 0.55 ⁇ m, the transparency properties and the durability properties are deteriorated.
  • the image-receptive coating is always applied to the backing film after the film has been completely processed.
  • the present inventors have now discovered a new type of transparent film having an image-receptive coating useful for producing an image on various copiers using a variety of toners with differing binder resins, with excellent toner adhesion, good image quality and good feedability, wherein the image-receptive coating is coated onto the film during the actual manufacturing of the film, rather than subsequent to the formation of the film.
  • the invention provides a transparent image-recording sheet suitable for use in a plain paper copier, comprising a transparent backing, bearing on at least one major surface thereof, a transparent water-based toner-receptive coating comprising:
  • Preferred image-recording sheets of the invention comprise a transparent backing bearing on at least one major surface thereof, a toner-receptive coating comprising:
  • image-recording sheets of the invention comprise a particulate filler system comprising at least one polymeric particle comprising:
  • the image-recording sheets of the invention comprise a bi-modal particulate filler system wherein at least one of the particles comprises a polymeric particle as described above.
  • the toner receptive layer can be coated out of a water-based emulsion or aqueous solution using well-known coating techniques.
  • the polar monomer is a cationic salt selected from the group consisting of wherein R is hydrogen or methyl, R 1 and R 2 may be hydrogen, identical or differing alkyl groups having up to about 8 carbon atoms, preferably up to about 2 carbon atoms, R 3 is an alkyl group having up to twenty carbon atoms containing a polar group such as -OH, -NH 2 , COOH, and X - is a halide.
  • R is hydrogen or methyl
  • R 1 and R 2 may be hydrogen, identical or differing alkyl groups having up to about 8 carbon atoms, preferably up to about 2 carbon atoms
  • R 3 is an alkyl group having up to twenty carbon atoms containing a polar group such as -OH, -NH 2 , COOH, and
  • X - is a halide.
  • the coating polymer can be prepared using any typical emulsion polymerization technique in an aqueous medium.
  • polymer includes both homopolymers and copolymers.
  • the term "manufacturing” means the actual making of the article, such as a film, rather than any post-processing steps.
  • orientation means stretching of a film, which may be either in a single “uniaxial” direction, or in two directions simultaneously “biaxially”.
  • Image-receptive sheets of the invention have a toner-receptive coating containing an image-receptive layer comprising from about 65 parts to about 99.9 parts of an imaging polymer.
  • the imaging polymer can be any polymer or polymer blend that can be coated out of a water-based emulsion of aqueous solution, using any well-known coating technique.
  • Such copolymer can be made from any ethylenically unsaturated monomers and can include acrylates and methacrylates, styrenes, substituted styrenes and vinylidine chlorides. These polymers can be subjected to stretching without adversely affecting the functional properties of the imaging layer.
  • the preferred imaging copolymer contains from about 80 parts to about 99 parts of at least one monomer selected from the group consisting of bicyclic alkyl (meth)acrylates, aliphatic alkyl (meth)acrylates having from about one to about twelve carbon atoms, styrenes, and aromatic (meth)acrylates.
  • Useful bicyclic alkyl(meth)acrylates include, but are not limited to dicyclopentenyl (meth)acrylate, norbornyl (meth)acrylate, 5-norborene-2-methanol, and isobornyl (meth)acrylate.
  • Preferred bicyclic monomers include dicyclopententyl (meth)acrylate, and isobornyl (meth)acrylate.
  • Useful aliphatic alkyl (meth)acrylates include, but are not limited to, methyl acrylate, ethyl acrylate, methyl (meth)acrylate, isobutyl (meth)acrylate, isodecyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like.
  • Preferred aliphatic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, and isodecyl (meth)acrylate.
  • Preferred copolymers contain at least one monomer selected from bicyclic alkyl (meth)acrylate, styrene, 2-phenoxyethyl(meth)acrylate, and isodecyl (meth)acrylate, as these monomers improve the adhesion of toner to the image receptive coating when used with most commercial copiers.
  • Particularly preferred copolymers contain at least one bicyclic (meth)acrylate or phenoxy(meth)acrylate, and the most preferred copolymers contain at least one bicyclic(meth)acrylate.
  • the bicyclic alkyl (meth)acrylates preferably comprise from about 10 parts to about 80 parts, more preferably from 20 parts to about 60 parts.
  • the preferred minimum amount is lower, i.e., about 5 parts, more preferably about 10 parts.
  • copiers have a styrene based toner system; the addition of styrene and substituted styrene monomers yield imaging sheets having very good toner 7 adhesion with such machines.
  • the copolymer must also contain from about 1 to about 20 parts of a polar monomer having the formula: wherein R is hydrogen or methyl, R 1 and R 2 is selected from the group consisting of hydrogen, identical, and differing alkyl groups having up to about 8 carbon atoms, preferably up to about 2 carbon atoms; the N-group can also comprise a cationic salt thereof.
  • Useful examples include N,N-dialkyl monoalkyl amino ethyl (meth)acrylate, and N,N-dialkyl monoalkyl amino methyl (meth)acrylate, N-butyl amino ethyl (meth)acrylate, and the like for emulsion polymers, and quaternary ammonium salts thereof for solution polymers.
  • Preferred monomers include N,N'-diethylaminoethyl(meth)acrylate, and N,N'-dimethylaminoethyl(meth)acrylate for emulsion polymers and bromoethanol salts of N,N'-dimethyl aminoethyl(meth)acrylate, and N,N'-diethyl aminoethyl(meth)acrylate for solution polymers.
  • the presence of these polar monomers improves the adhesion of the toner receptive coating to the transparent film substrate or backing.
  • most preferred copolymers also comprise at least one monomer selected from aliphatic alkyl (meth)acrylate monomers.
  • Polymeric particles useful in the present invention can range from about 1 ⁇ m to about 15 ⁇ m in diameter and can include poly(methylmethacrylate) (PMMA), modified poly(methylmethacrylate), poly(tetrafluorethylene), polyethylene, particles produced from diol di(meth)acrylate homopolymers which impart antifriction characteristics when coated on image recording sheets. These diol di(meth)acrylates can be reacted with long-chain fatty alcohol esters of (meth)acrylic acid.
  • Preferred embodiments contain particles selected from PMMA, modified PMMA, and particles produced from either diol-di(meth)acrylate homopolymers or copolymers of diol di(meth)acrylates and long-chain fatty alcohol esters of (meth)acrylic acid.
  • Examples of these monomers include those selected from the group consisting of 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, and mixtures thereof.
  • Preferred monomers include those selected from the group consisting of 1,4-butanediol di(meth)acrylate, 1,6 hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, and 1,14-tetradecanediol di(meth)acrylate.
  • Useful long-chain monomers include, but are not limited to lauryl (meth)acrylate, octadecyl (meth)acrylate, stearyl (meth)acrylate, and mixtures thereof, preferably stearyl (meth)acrylate.
  • the microspheres may optionally contain up to about 30 percent by weight of at least one copolymerized ethylenically unsaturated monomer selected from the group consisting of vinyl esters such as vinyl acetate, vinyl propionate, and vinyl pivalate; acrylic esters such as methacrylate, cyclohexylacrylate, benzylacrylate, isobornyl acrylate, hydroxybutylacrylate and glycidyl acrylate; methacrylic esters such as methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, ⁇ -methacryloxypropyl trimethoxysilane, and glycidyl methacrylate; styrene; vinyltoluene; ⁇ -methyl styrene, and mixtures thereof.
  • vinyl esters such as vinyl acetate, vinyl propionate, and vinyl pivalate
  • acrylic esters such as methacryl
  • Highly preferred beads include those comprising 50/50 poly(hexanediol-diacrylate/stearyl methacrylate), and 50/50 poly(butanediol-diacrylate) ⁇ lauryl(meth)acrylate, 80/20 poly(hexanedioldiacrylate)/stearyl(meth)acrylate, 50/50 polymethylmethacrylate/ 1,6 hexanedioldiacrylate, C 14 dioldiacrylate, C 12 dioldi(meth)acrylate, and 40/50/10 poly(hexanedioldiacrylate)/stearyl(meth)acrylate/ glycidyl(meth)acrylate.
  • beads of the present invention may also optionally comprise additives which are not ethylenically unsaturated, but which contain functional groups capable of reacting with materials containing reactive groups which may also be coated on the substrate along with the anti-friction beads.
  • additives are useful in modifying the degree of interaction or bonding between the beads and the imaging polymer.
  • Suitable examples include organosilane coupling agents having alkyl groups with 1 to about 8 carbon atoms, such as glycidoxy trimethoxysilanes such as ⁇ -glycidoxypropyl-trimethoxysilane, and (aminoalkylamino) alkyl trimethoxysilanes such as 3-(2-amino ethyl amino) propyl trimethoxysilane.
  • the mean particle size preferably ranges from about 1 ⁇ m to about 15 ⁇ m. Particles smaller than 1 ⁇ m would require the use of more particles to produce an effective coefficient of friction, this would tend to also produce more haze. Larger particles than 15 ⁇ m would require thicker coatings to anchor the particles firmly in the coatings, which would increase haze and coating cost.
  • the particles preferably have narrow particle size distributions, i.e., a standard deviation of up to 20% of the average particle size. These ranges are preferably 1-6 ⁇ m, 3-6 ⁇ m, 4-8 ⁇ m, 6-10 ⁇ m, 8-12 ⁇ m, 10-15 ⁇ m.
  • a particle system containing more than one particle wherein the particles have a bimodal particle size distribution. This is done by mixing particles having 2 different particle size distributions such as particles having a distribution of sizes from 1-4 ⁇ m mixed with 6-10 ⁇ m.
  • both particles can be selected from the preferred polymeric beads described above, or one of the particles can be selected from such preferred beads and one selected from other beads such as PMMA and modified PMMA beads, the second type of bead also preferably having a narrow particle size distribution.
  • particles having a size smaller than 1 ⁇ m can be used as one of the particles.
  • a particle having a size of from about 0.1 ⁇ m to about 0.7 ⁇ m can be mixed with a particle having a size of from about 1 ⁇ m to about 6 ⁇ m.
  • both bimodal particles are selected from beads produced from the copolymer of hexanedioldiacrylate and stearylmethacrylate, having particle size distributions of from about 1 to about 4 ⁇ m and from about 6 to about 10 ⁇ m, or from about 2 to about 6 ⁇ m and from about 8 to about 12 ⁇ m, or from about 0.20 to 0.5 ⁇ m and from about 1-6 ⁇ m.
  • Coatings for the final image-receptive sheets useful for copying devices typically range in thickness from 100nm to 1500nm, preferably 200nm to 500nm. If large particles are used, then the coating thickness must be increased accordingly to ensure that enough coating material is present to anchor the particles onto the transparent substrate, while the coating thickness can be correspondingly lowered for smaller particles. Hence the most preferred particle size distributions chosen reflect more on the coating thickness than the feeding performance of other larger particle sizes and vice versa.
  • microspheres are polymerized by means of conventional free-radical polymerization, e.g., those suspension polymerization methods described in U.S. Patent No. 4,952,650, and 4,912,009, incorporated herein by reference, or by suspension polymerization using a surfactant as the suspending agent, and use those initiators normally suitable for free-radical initiation of acrylate monomers.
  • These initiators include azo compounds such as 2,2-azobis(2-methyl butyronitrile) and 2,2-azobis(isobutyronitrile); and organic peroxides such as benzoylperoxide and lauroylperoxide.
  • suspension polymerization is used wherein the suspending agent is a surfactant.
  • An antistatic agent may also be present in the toner receptive layer.
  • Useful agents are selected from the group consisting of nonionic antistatic agents, cationic agents, anionic agents, and fluorinated agents.
  • Useful agents include such as those available under the trade name AMTERTM, e.g., AMTERTM 110, 1002, 1003, 1006, and the like, derivatives of JeffamineTM ED-600, 900, 2000, and 4,000, with FX8 and FX10, available from 3M, LarostatTM 60A, and MarkastatTM AL-14, available from Mazer Chemical Co., with the preferred antistatic agents being steramido-propyldimethyl- ⁇ -hydroxy-ethyl ammonium nitrate, available as CyastatTM SN, N,N'-bis(2-hydroxyethyl)-N-(3'-dodecyloxy-2'2-hydroxylpropyl) methylammonium methylsulfate, available as CyastatTM 609,
  • an emulsifier must also be present.
  • emulsifiers include nonionic, or anionic emulsifiers, and mixtures thereof, with nonionic emulsifiers being preferred.
  • Suitable emulsifiers include those having a HLB of at least about 10, preferably from about 12 to about 18.
  • Useful nonionic emulsifiers include C 11 to C 18 polyethylene oxide ethanol, such as TergitolTM especially those designated series "S" from Union Carbide Corp, those available as TritonnTM from Rohm and Haas Co., and the TweenTM series available from ICI America.
  • Useful anionic emulsifiers include sodium salts of alkyl sulfates, alkyl sulfonates, alkylether sulfates, oleate sulfates, alkylarylether sulfates, alkylarylpolyether sulfates, and the like.
  • commercially available examples include such as those available under the trade names SiponateTM and SiponicTM from Alcolac, Inc.
  • the emulsifier When used, the emulsifier is present at levels of from about 1% to about 7%, based on polymer, preferably from about 2% to about 5%.
  • Additional wetting agents with HLB values of 7-10 may be present in the emulsion to improve coatability. These additional surfactants are added after polymerization is complete, prior to coating of the polymeric substrate.
  • Preferred additional wetting agents include fluorochemical surfactants such as wherein n is from about 6 to about 15 and R can be hydrogen or methyl.
  • Useful examples include FC-170C and FC-171, available from 3M.
  • Another useful wetting agent is TritonTM X-100, available from Union Carbide.
  • Addition of a coalescing agent is also preferred for emulsion based image receptive layers to insure that the coated material coalesces to form a continuous and integral layer and will not flake in conventional copiers under copying and fixing conditions.
  • Compatible coalescing agents include propylcarbitol, available from Union Carbide as the CarbitolTM series, as well as the CellusolveTM series, PropasolveTM series, EktasolveTM and Ektasolve series of coalescing agents, also from Union Carbide.
  • Other useful agents include the acetate series from Eastman Chemicals Inc., the DowanolTM E series, DowanolTM E acetate series, DowanolTM PM series and their acetate series from Dow Chemical, N-methyl-2-pyrrolidone from GAF, and 3-hydroxy-2,2,4-trimethyl pentyl isobutryate, available as TexanolTM, from Eastman Chemicals Inc. These coalescing agents can be used singly or as a mixture.
  • Useful additives include such as catalysts, thickeners, adhesion promotors, glycols, defoamers and the like.
  • One preferred optional ingredient in the emulsion polymerized embodiment of the invention is an additional adhesion promotor to enhance durability of thicker coatings to the substrate.
  • Useful adhesion promotors include organofunctional silanes having the following general formula: wherein R 1 , R 2 , and R 3 are selected from the group consisting of an alkoxy group and an alkyl group with the proviso that at least one alkoxy group is present, n is an integer from 0 to 4, and Y is an organofunctional group selected from the group consisting of chloro, methacryloxy, amino, glycidoxy, and mercapto.
  • Useful silane coupling agents include such as ⁇ -aminopropyl trimethoxysilane, vinyl triethoxy silane, vinyl tris( ⁇ -methoxy ethoxy)-silane, vinyl triacetoxy silane, ⁇ -methacryloxypropyltrimethyoxy silane, ⁇ -( ⁇ -aminoethyl)aminopropyl trimethoxysilane, and the like.
  • the adhesion promotor may be present at levels of from about 0.5 to about 15% of the total resin, preferably from about 4% to about 10%.
  • Film substrates may be formed from any polymer capable of forming a self-supporting sheet, e.g., films of cellulose esters such as cellulose triacetate or diacetate, polystyrene, polyamides, vinyl chloride polymers and copolymers, polyolefin and polyallomer polymers and copolymers, polysulphones, polycarbonates, polyesters, and blends thereof.
  • cellulose esters such as cellulose triacetate or diacetate, polystyrene, polyamides, vinyl chloride polymers and copolymers, polyolefin and polyallomer polymers and copolymers, polysulphones, polycarbonates, polyesters, and blends thereof.
  • Suitable films may be produced from polyesters obtained by condensing one or more dicarboxylic acids or their lower alkyl diesters in which the alkyl group contains up to about 6 carbon atoms, e.g., terephthalic acid, isophthalic, phthalic, 2,5-,2,6-, and 2,7-naphthalene dicarboxylic acid, succinic acid, sebacic acid, adipic acid, azelaic acid, with one or more glycols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and the like.
  • dicarboxylic acids or their lower alkyl diesters in which the alkyl group contains up to about 6 carbon atoms, e.g., terephthalic acid, isophthalic, phthalic, 2,5-,2,6-, and 2,7-naphthalene dicarboxylic acid, succinic acid, sebacic acid, adipic acid
  • Preferred film substrates or backings are cellulose triacetate or cellulose diacetate, poly(ethylene naphthalate), polyesters, especially poly(ethylene terephthalate), and polystyrene films. Poly(ethylene terephthalate) is most preferred. It is preferred that film backings have a caliper ranging from about 50 ⁇ m to about 200 ⁇ m. Film backings having a caliper of less than about 50 ⁇ m are difficult to handle using conventional methods for graphic materials. Film backings having calipers over 200 ⁇ m are stiffer, and present feeding difficulties in certain commercially available copying machines. However, the preferred caliper varies with the type of copying machine and its requirements, with e.g., color copiers easily handling thick backings.
  • polyester film substrates When polyester film substrates are used, they can be biaxially oriented to impart molecular orientation, and may also be heat set for dimensional stability during fusion of the image to the support. These films may be produced by any conventional extrusion method.
  • the polyester film is formed by extrusion or casting.
  • the imaging layer is coated thereon immediately subsequent to the forming. After coating, it is dried in an oven and then either uniaxially oriented in the machine direction to produce a finished product, or simultaneously biaxially oriented to produce a finished product.
  • the polyester film is extruded or cast, and uniaxially oriented in the machine direction.
  • the imaging layer is coated thereon immediately subsequent in the processing line. After coating, it is dried in an oven, and then further oriented in the transverse direction to produce a finished product.
  • the use of large polymeric beads does not significantly affect the optical properties of the final, transparent image-receptive sheet even through the image-receptive layer is stretched after coating.
  • the coated layer exhibits evidence of such stretching under optical microscopy, but surprisingly, the coating remains transparent, and the polymer, whether emulsion or solution polymerized, exists in a continuous coated layer without voids, thus showing the high integrity and cohesiveness of the coated layer.
  • a second imaging layer can be coated onto the opposing surface of the film and dried.
  • This second layer can be an identical or different composition to the first layer.
  • Image-recording sheets of the invention surprisingly do not require a primer layer or surface treatment such as corona treatment in order to exhibit good adhesion of the receptive layer to the film substrate, which is common in products of this type.
  • the image-recording sheet of the invention may also comprise an ink-permeable protective layer such as polyvinyl alcohol, and the like, to insure faster drying.
  • an ink-permeable protective layer such as polyvinyl alcohol, and the like, to insure faster drying.
  • Such layers can be coated onto the imaging layer either prior to, or after, transverse orientation. If applied before transverse orientation, an uncrosslinked layer is preferred.
  • Image-receptive sheets of the invention are particularly useful in the production of imaged transparencies for viewing in a transmission mode or a reflective mode, i.e., in association with an overhead projector.
  • COF Coefficient of Friction
  • the bead-coated sides of two sheets are brought into contact with each other, with 1 sheet attached to a 1 kg brass sled, tethered to a force gauge and the second sheet attached to the moveable platen.
  • the platen is drawn at a constant speed of 15.24 cm/min., and the maximum and average COF values are obtained from the tester readout and recorded.
  • ASTM D2197-86 "Adhesion of Organic Coatings by Scope Adhesion" was used to measure toner adhesion to the coated surface of the film. The measurements were done on samples after the coated film was imaged on a variety of commercially available copiers, specifically Xerox 5065. The results were recorded in grams. A measurement of about 200 g or more is acceptable.
  • Haze is measured with the Gardner Model XL-211 Hazeguard hazemeter or equivalent instrument. The procedure is set forth in ASTM D 1003-61 (Reapproved 1977). This procedure measures haze, both of the unprocessed film (precopy) and the post copy film, as noted hereinafter.
  • Durability is measured using the SP-102B-3M90 Slip/Peel Tester available from Imass, equipped with an MB-5 load cell. The platen speed was set at 15.24 cm/minute. A 1 cm x 2 cm rubber was attached by a piece of double-coated tape to the middle of the sled with the 2 cm side parallel to the direction of the sliding motion. Test samples of the image receptive film were cut into 5 cm x 20 cm and 2.5 by 5 cm pieces.
  • the 5 cm x 20 cm test piece is attached with double-coated tape to the left end of the platen and both sides of the 200 g sled weight just above and below the 1 cm x 2 cm rubber,
  • the 2 cm x 5 cm test piece is then attached to the 200 g sled such that the 2 cm side is parallel to the 5 cm side of the rubber.
  • Both test pieces are pressed to assure that they are flat and centered. They are then labeled and marked.
  • One end of a 20 cm long 12 Kg steel finishing line leader was permanently connected to the 200 g sled and the other end to the load cell. The sled is positioned above the left end of the platen and aligned with it to assure that the leader is in a relaxed state.
  • the sled is then gently laid onto the test sample. 500 g of additional weight is added to the sled and the platen is activated. After travelling for a distance of about 8 cm, the platen is stopped and the sample removed to rate the durability.
  • the ratings are according to the following scale:
  • This test defines the number of failures per 100 sheets fed. Receptor sheets were conditioned in a stack at a temperature of 25°C and 50% relative humidity, overnight prior to feed testing. Any jamming, misfeed or other problems during the copying process was recorded as a failure.
  • Polymeric beads having other compositions could also be prepared using such a procedure. These include beads having varying ratios of hexanedioldiacrylate and stearyl methacrylate, mixtures of BDDA and SMA, BDDA and lauryl acrylate, and the like.
  • a coarse emulsion was obtained, which was then passed through a Manton-Gaulin Homogenizer from Gaulin Corp. at 500 psi. The emulsion was passed through the homogenizer a second time. The homogenized emulsion was then returned to the resin flask and heated to 60°C. It was maintained at the temperature for 15 hours under gentle agitation (400-500 rpm) with a nitrogen blanket. A stable emulsion was obtained having about 30% submicron polymeric beads. Analysis on a Coulter N4 from Coulter Electronics, Inc. revealed an average particle size of 0.25 ⁇ m.
  • An emulsion polymer was prepared according to the following procedure:
  • Deionized water (DI water) and surfactant (Triton X405) were charged into a four-neck flask equipped with a reflux condenser, thermometer, stirrer, metering pump and a nitrogen gas inlet. This was stirred and heated to 70°C under nitrogen atmosphere.
  • the monomers, IBOA, MMA, EA, DMAEMA and carbon tetrabromide (a chain transfer agent) were pre-mixed in a separate container at room temperature to make the monomer premix.
  • the reaction temperature leveled off at 70°C 20% of the monomer premix and the initiator (ammonium persulfate) were charged into the reactor to start the polymerization.
  • the reaction was allowed to exotherm. At the exotherm peak, the remaining 80% monomer premix was fed into the reaction using a metering pump over a two-hour period while the reaction temperature was maintained at 70°C. After the monomer addition, the polymerization was continued for two hours at 70°C to eliminate residual monomers. The latex was then cooled to 25°C and filtered through a 25 ⁇ m filter.
  • PET film A 1200 ⁇ m thick polyethylene terephthalate (PET) film was extruded at temperatures of about 250-300°C onto a casting wheel at a speed of about 25 meters/minute. It was then uniaxially oriented in the machine direction about 3.2 times. The solution from Part C was then coated onto one of the sides of the film and dried in an oven at about 75°C for about 10 seconds, yielding a dry coating weight of about 1.100 grams/meter 2 .
  • PET polyethylene terephthalate
  • the film was identically coated on the opposing side, that coating was then dried in the same manner.
  • the film was oriented in the transverse direction 4.75 times to yield a dry coating weight of about 0.21 g/sq meter on each side.
  • Example 1 This example was made in the following manner using the same emulsion polymer as Example 1:
  • This example was also coated and tested according to Example 1 and the results are shown in Tables 2 and 3.
  • the coating toughness value is slower in this case because of the extremely thin coating weight of the water-based ink-receptive coating.
  • Example 3 was made in the following manner using the same emulsion polymer as Example 1.
  • each premix was measured to verify that they were 25%, 0.87 kg of the 0.25 ⁇ m premix and 4.36 kg of the 8 ⁇ m pre-mix were weight from their respective master batches and combined with 454 g of FC-170C (10% in water) and 0.91 kg TX-100 in a separate container. This mixture was mixed for 15 minutes before addition to the coating solution which is described below.
  • the formulation shown below in Table 4 was admixed and coated using a procedure similar to that disclosed in the previous examples.
  • the binder in this case is a copolymer of vinylidine chloride (90%), ethyl acrylate (9%) and itaconic acid (1%).
  • Table 4 Coating Formulation Weight (kg) % Solids % of Total Latex Binder 33.3 21 94.44 6 ⁇ m PSMA Beads 0.80 25 2.27 0.25 ⁇ m PSMA Beads 0.16 25 0.45 FC-170C Surfactant 1.0 10 2.84
  • PET film was extruded onto a casting wheel at 24 ft/min.
  • the thickness of the cast film was 1500 ⁇ m. It was then uniaxially oriented 3.2 times after which the line speed was about 24 meters/min.
  • the film was coated on one side and dried at 75°C for 20 seconds. The opposite side was then coated and dried using similar conditions. The air knife coating technique was used to apply and meter the solution onto the web. The coated film was then oriented in the transverse direction 4.8 times yielding the finished 100 ⁇ m film with a single side coating weight of 0.14 gms/meter 2 Testing results are shown in Tables 6 and 7.
  • Example 5 The feeding failures for Example 5 are higher than acceptable, as an extremely low amount of antistatic agent was used, which resulted in low conductivity. A higher amount of antistatic agent used with an otherwise identical formulation would result in an acceptable failure rate for feedability.
  • Example 2 This was made in the same manner as Example 1, except that 11 ⁇ m PMMA and 5 ⁇ m 97/3 PMMA/HEMA beads were used in place of the SMA beads. This was tested and the results are reported in Tables 5 and 6.
  • the emulsion polymer was diluted with D.I. water to a solids content of about 19.5% and coated onto a 500 micrometer thick PET film at a coating weight of about 0.042 g/m 2 .
  • the coated sample was then dried at about 0°C for 10 minutes and then simobiaxially oriented (stretching in 2 directions at the same time) at 110°C to yield a 50 micrometer thick coated film.
  • the stretched film was then heat set for 15 seconds at 240°C and laminated to a 50 micrometer thick PET film.
  • the sample was tested for toner adhesion using a XeroxTM model 5065 copier according to the test method described above. The results are shown in table 7.
  • Table 7 Example No. DMAEMA EA MMA Add.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Claims (19)

  1. Feuille transparente d'enregistrement d'images convenant pour être utilisée dans un copieur à papier ordinaire, comprenant un support transparent possédant deux surfaces principales, ladite feuille ayant une direction machine et une direction transversale, au moins l'une desdites surfaces principales étant recouverte par un revêtement transparent à base d'eau, réceptif pour le toner, comprenant :
    a) entre environ 65 et environ 99,9 parties d'un polymère apte à former une image;
    b) entre environ 0,1 et environ 15 parties de particules d'au moins un polymère ayant une taille moyenne de particules comprise entre environ 1 µm et environ 15 µm, et
    c) entre 0 et environ 20 parties d'un agent antistatique,
    ledit revêtement réceptif pour le toner étant déposé sur ledit support transparent à un instant pendant la fabrication dudit revêtement, choisi dans le groupe
    a) avant toute orientation dudit film, et
    b) après une orientation uniaxiale dans ladite direction machine.
  2. Feuille transparente d'enregistrement d'images selon la revendication 1, dans laquelle ledit revêtement transparent à base d'eau réceptif pour le toner comprend entre environ 65 et environ 99,9 parties d'un copolymère de formation d'images formé par
    1) entre environ 80 parties et environ 99 parties d'au moins un monomère choisi dans le groupe constitué par des (méth)acrylates d'alkyles bicycliques, des (méth)acrylates d'alkyles aliphatiques, lesdits alkyles aliphatiques possédant entre environ 1 et environ 12 atomes de carbone, des (meth)acrylates aromatiques, et
    2) entre environ 1 partie et environ 20 parties d'un monomère polaire répondant à la formule :
    Figure imgb0009
     R représentant l'hydrogène groupe méthyle, R1 et R2 étant choisis dans le groupe comprenant l'hydrogène, des groupes alkyle identiques et des groupes alkyle différents ayant jusqu'à environ 8 atomes de carbone, de préférence jusqu'à environ 2 atomes de carbone, le groupe N pouvant également comporter un sel cationique de ces derniers, n étant égal à 1 ou 2.
  3. Feuille transparente d'enregistrement d'images selon la revendication 1, comprenant en outre
    a) entre environ 0,1 et environ 15 parties de particules polymères comprenant
    1) au moins environ 20 parties en poids d'un di(méth)acrylate de diol polymérisé répondant à la formule

            CH2+CR2COOCnH2nOOCR2=CH2

    R2 désignant l'hydrogène ou un groupe méthyle, et n étant un entier compris entre environ 4 et environ 18,
    2) entre 0 et environ 80 parties d'au moins un monomère de vinyle copolymérisé répondant à la formule

            CH2=CR2COOCmH2m+1

    R2 représentant un hydrogène ou un groupe méthyle et m étant un entier compris entre environ 12 et environ 40, et
    3) entre 0 et environ 30 parties d'au moins un monomère copolymérisé insaturé par de l'éthylène, choisi dans le groupe comprenant des esters vinyliques, des esters acryliques, des esters méthacryliques, le styrène, des dérivés de ces produits et des mélanges de ces produits, a, b et c formant un total de 100 parties, et
    b) entre 0 et environ 20 parties d'un agent antistatique choisi dans le groupe comprenant des agents cationiques, des agents anioniques, des agents fluorés et des agents non ioniques.
  4. Feuille transparente d'enregistrement d'images selon la revendication 1, dans laquelle ledit revêtement à base d'eau et réceptif au toner est déposé sur ledit support transparent avant toute orientation dudit film.
  5. Feuille transparente d'enregistrement d'images selon la revendication 1, dans laquelle ledit revêtement à base d'eau, réceptif pour le toner, est déposé sur ledit support transparent après une orientation uniaxiale dudit film dans la direction machine.
  6. Feuille transparente d'enregistrement d'images selon l'une quelconque des revendications 1 à 5, dans laquelle ladite feuille est en outre soumise à une orientation dans ladite direction transversale après que ledit revêtement à base d'eau et réceptif au toner a été déposé sur cette feuille.
  7. Feuille transparente d'enregistrement d'images selon l'une quelconque des revendications 1 à 6, dans laquelle ladite feuille comporte en outre un revêtement réceptif pour le toner situé sur ladite seconde surface principale.
  8. Feuille transparente d'enregistrement d'images selon la revendication 7, dans laquelle ledit revêtement réceptif pour le toner situé sur ladite seconde surface principale est un revêtement à base d'eau réceptif pour le toner.
  9. Feuille transparente d'enregistrement d'images selon les revendications 7 ou 8, dans laquelle ledit revêtement réceptif pour le toner, situé sur ladite seconde surface, est déposé sur cette surface après que ladite feuille a été soumise à une orientation transversale.
  10. Feuille transparente d'enregistrement d'images selon les revendications 7 ou 8, dans laquelle ledit revêtement réceptif pour le toner, situé sur ladite seconde surface, est déposé sur cette dernière après que ladite feuille a été soumise à une orientation uniaxiale.
  11. Feuille transparente d'enregistrement d'images selon la revendication 1 ou 2, dans laquelle ledit copolymère de formation d'images comprend un acrylate d'alkyle aliphatique choisi dans le groupe comprenant l'acrylate de méthyle, l'acrylate d'éthyle, le méthyleméthacrylate, l'éthyleméthacrylate, l'acrylate d'isobutyle, le méthacrylate d'isobutyle, le méthacrylate d'isodécyle et l'acrylate d'isobutyle.
  12. Feuille transparente d'enregistrement d'images selon la revendication 1, 2 ou 11, dans laquelle ledit copolymère de formation d'images comporte en outre un monomère choisi dans le groupe comprenant le styrène, le styrène substitué et des esters vinyliques.
  13. Feuille transparente d'enregistrement d'images selon la revendication 1, dans laquelle ledit agent antistatique est choisi dans le groupe comprenant le nitrate de stéramido-propyldiméthyle- -hydroxyéthylammonium, le méthylsulfate de N,N'-bis(2-hydroxyéthyl)-N-(3'-dodécyloxy-2'2-hydroxylpropyl) méthyle ammonium et des mélanges de ces produits.
  14. Feuille transparente d'enregistrement d'images selon la revendication 1 ou 3, dans laquelle ladite particule polymère est choisie dans le groupe comprenant une particule de 50/50 poly(hexanedioldiacrylate / méthacrylate de stéaryle), une particule de 50/50 poly(butanedioldiacrylate)/(méth)acrylate de lauryle, une particule de 80/20 poly(hexanedioldiacrylate/(meth)acrylate de stéaryle , une particule de 50/50 polyméthyleméthacrylate/1,6 hexanedioldiacrylate, une particule de C14 dioldiacrylate, une particule de C12 dioldi(meth)acrylate, et une de particule 40/50/10 poly(hexanedioldiacrylate)/(méth)acrylate de stéaryle/(meth)acrylate de glycidyle.
  15. Feuille transparente d'enregistrement d'images selon la revendication 14, comportant en outre une particule polymère additionnelle contenant environ 50 à environ 80 parties d'hexanedioldiacrylate et environ 50 à environ 20 parties de méthacrylate de stéaryle, ladite particule ayant une taille moyenne comprise entre environ 0,25 m et environ 15 µm.
  16. Feuille transparente d'enregistrement d'images selon l'une quelconque des revendications 1 à 15, comprenant en outre un additif choisi dans le groupe comprenant des agents de coalescence, des agents de mouillage, des agents de recirculation, des catalyseurs, des épaississants, des promoteurs d'adhérence, des glycols et des agents antimousse.
  17. Feuille transparente d'enregistrement d'images selon l'une quelconque des revendications 1 à 16, dans laquelle ledit substrat est choisi dans le groupe comprenant des polyesters, du poly(naphtalate d'éthylène), des polystyrènes, du triacétate de cellulose et des mélanges de ces produits.
  18. Procédé pour fabriquer la feuille transparente d'enregistrement d'images selon la revendication 1, comprenant les étapes consistant à
    a) former ledit substrat au moyen d'un procédé choisi parmi l'extrusion et la coulée, ledit substrat possédant une première face et une seconde face, une direction machine et une direction transversale,
    b) orienter d'une manière uniaxiale ledit substrat par étirage, dans ladite direction machine,
    c) recouvrir ladite couche de formation d'images située sur ladite première face et le faire sécher pour former ladite feuille d'enregistrement d'images, et
    d) orienter ladite feuille d'enregistrement d'images par étirage dans ladite direction transversale.
  19. Procédé pour fabriquer la feuille transparente de formation d'images selon la revendication 1, comprenant les étapes consistant à
    a) former ledit substrat au moyen d'un procédé choisi parmi l'extrusion et la coulée, ledit substrat possédant une première face et une seconde face, une direction machine et une direction transversale,
    b) recouvrir ladite couche de formation d'images située sur ladite première face et la faire sécher de manière à former ladite feuille d'enregistrement d'images,
    c) déposer un revêtement réceptif pour le toner sur ladite seconde surface principale,
    d) orienter uniaxialement ledit substrat par étirage, dans ladite direction machine, et
    e) orienter ladite feuille d'enregistrement d'images par étirage dans ladite direction transversale.
EP19930402259 1992-09-18 1993-09-16 Feuille réceptrice d'images pour copieurs sur papier ordinaire Expired - Lifetime EP0588724B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US947252 1986-12-29
US07/947,252 US5310595A (en) 1992-09-18 1992-09-18 Water-based transparent image recording sheet for plain paper copiers
US08/030,699 US5310591A (en) 1992-09-18 1993-03-12 Image-receptive sheets for plain paper copiers
US30699 1993-03-12

Publications (2)

Publication Number Publication Date
EP0588724A1 EP0588724A1 (fr) 1994-03-23
EP0588724B1 true EP0588724B1 (fr) 1997-05-14

Family

ID=26706359

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19930402259 Expired - Lifetime EP0588724B1 (fr) 1992-09-18 1993-09-16 Feuille réceptrice d'images pour copieurs sur papier ordinaire

Country Status (7)

Country Link
US (1) US5310591A (fr)
EP (1) EP0588724B1 (fr)
JP (1) JP3469920B2 (fr)
KR (1) KR100276366B1 (fr)
AU (1) AU669553B2 (fr)
CA (1) CA2105909C (fr)
DE (1) DE69310653T2 (fr)

Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5518809A (en) * 1992-09-18 1996-05-21 Minnesota Mining And Manufacturing Company Water-based transparent image recording sheet for plain paper copiers
US5500925A (en) * 1992-12-01 1996-03-19 Xaos Tools Dynamic image processing using particle systems
US5407234A (en) * 1992-12-11 1995-04-18 Avery Dennison Corporation Permanent xerographic toner-receptive index divider
US5411787A (en) * 1993-10-19 1995-05-02 Minnesota Mining And Manufacturing Company Water based transparent image recording sheet
US5445866A (en) * 1993-10-19 1995-08-29 Minnesota Mining And Manufacturing Company Water-based transparent image recording sheet
FR2719523B1 (fr) * 1994-05-04 1996-07-19 Smic Sa Imprimerie Procédé permettant la reproduction en couleur de supports en matériau plastique préalablement imprimés, et moyens de mise en Óoeuvre du procédé.
FR2725051B1 (fr) * 1994-09-28 1997-01-03 Rhone Poulenc Films Elements transparents pour photocopie electrostatique
US5569485A (en) * 1994-10-07 1996-10-29 Minnesota Mining And Manufacturing Company Method for the manufacture of a radiographic intensifying screen with antistat
US5411806A (en) * 1994-10-07 1995-05-02 Minnesota Mining And Manufacturing Company Method for the manufacture of a phosphor screen and resulting article
DE4439031C2 (de) 1994-11-02 1996-08-22 Siegfried Lanitz Polymerbeschichtetes Mehrschichtmaterial und Verfahren zu seiner Herstellung
EP0792319A1 (fr) * 1994-11-18 1997-09-03 Minnesota Mining And Manufacturing Company Feuille transparente a base d'eau pour l'mpression d'images, destinee a des photocopieurs a papier ordinaire
US5500457A (en) * 1994-11-18 1996-03-19 Minnesota Mining And Manufacturing Company Water based toner receptive core/shell latex compositions
EP0761460B1 (fr) * 1995-08-07 1999-05-06 Tokuyama Corporation Feuille pour l'impression par jet d'encre
MY129788A (en) 1996-01-25 2007-04-30 Innovia Films Ltd Printable film.
US5709926A (en) * 1996-07-18 1998-01-20 Hoechst Diafoil Company Reclaimable transparencies for plain paper copiers
US5925447A (en) * 1996-07-18 1999-07-20 Mitsubishi Polyester Film, Llc Permanent antistatic coating and coated polymeric film
US6238785B1 (en) * 1996-10-04 2001-05-29 Oji-Yuka Synthetic Paper Co., Ltd. Thermoplastic resin film with excellent printability
US5763056A (en) * 1997-01-31 1998-06-09 Minnesota Mining And Manufacturing Company Light blocking transparency assembly
US5965226A (en) * 1997-03-11 1999-10-12 Mitsubishi Polyester Film, Llc In-line method for laminating silicone-coated polyester film to paper, and laminate produced thereby
WO1999044098A1 (fr) * 1998-02-25 1999-09-02 Minnesota Mining And Manufacturing Company Dispositif de protection pour transparents de retroprojecteurs
JP2003514977A (ja) * 1999-11-22 2003-04-22 スリーエム イノベイティブ プロパティズ カンパニー 水をベースとするコーティング組成物
US6290434B1 (en) * 1999-12-30 2001-09-18 Hylsa, S.A. De C.V. Expansion joint for high-pressure high-temperature pneumatic transport of DRI or other abrasive particles
ATE304453T1 (de) * 2000-02-08 2005-09-15 3M Innovative Properties Co Verbesserte verfahren für kalten bildtransfer
US6764725B2 (en) 2000-02-08 2004-07-20 3M Innovative Properties Company Ink fixing materials and methods of fixing ink
GB2375992A (en) * 2001-06-01 2002-12-04 Ilford Imaging Uk Ltd Recording method
US6926957B2 (en) 2001-06-29 2005-08-09 3M Innovative Properties Company Water-based ink-receptive coating
CA2449938A1 (fr) 2001-07-25 2003-02-06 Avery Dennison Corporation Pelures de papier synthetique et procedes de fabrication
US20030175451A1 (en) 2002-03-12 2003-09-18 Palitha Wickramanayake Chemically-bonded porous coatings that enhance humid fastness and fade fastness performance of ink jet images
AU2004221871A1 (en) 2003-03-13 2004-09-30 Avery Dennison Corporation Thermal transfer image receiving sheet and method
US20040219379A1 (en) * 2003-04-30 2004-11-04 Oji Paper Co., Ltd. Electrophotographic recording sheet
WO2005007304A1 (fr) * 2003-07-16 2005-01-27 Hewlett-Packard Development Company, L.P. Revetement de substrat ameliorant l'adherence d'un toner
US8088860B2 (en) * 2004-10-29 2012-01-03 Hewlett-Packard Development Company, L.P. Paper with photo-feel backcoat
US20070048466A1 (en) * 2005-09-01 2007-03-01 Huynh Dieu D Thermal transfer image receiving sheet and method
ITPD20070106A1 (it) 2007-03-23 2008-09-24 Geox Spa Sottopiede di montaggio impermeabile all'acqua e permeabile al vapord'acqua e calzatura realizzata con detto sottopiede
US8449970B2 (en) 2007-07-23 2013-05-28 3M Innovative Properties Company Antistatic article, method of making the same, and display device having the same
KR101144490B1 (ko) * 2010-08-27 2012-05-11 신동식 튜닝 기능을 갖는 알에프카드모듈
TWI503346B (zh) * 2014-06-11 2015-10-11 Zirco Applied Materials Co Ltd 近紅外光屏蔽膜及近紅外光屏蔽膜之製造方法
US9599918B2 (en) * 2015-04-09 2017-03-21 Xerox Corporation Clear toner compositions

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3539340A (en) * 1967-07-17 1970-11-10 Celanese Corp Transparencies for electrostatic copying consisting of polyester sheets coated with vinylidene chloride copolymers
CA977596A (en) * 1971-12-28 1975-11-11 Yoshio Tsuji Imaged sheet or film and method and apparatus for preparing same
US4071362A (en) * 1973-01-05 1978-01-31 Fuji Photo Film Co., Ltd. Electrophotographic copying film
US4085245A (en) * 1976-04-15 1978-04-18 Xerox Corporation Transparencies for color xerographic copies
US4259422A (en) * 1978-04-28 1981-03-31 Eastman Kodak Company Electrographic process for making transparencies
US4480003A (en) * 1982-09-20 1984-10-30 Minnesota Mining And Manufacturing Company Construction for transparency film for plain paper copiers
US4745019A (en) * 1983-05-16 1988-05-17 American Hoechst Corporation Graphic film having a copolyester primed polyester film as its substrate
US4585687A (en) * 1983-05-16 1986-04-29 American Hoechst Corporation Copolyester primed polyester film
US4493872A (en) * 1983-12-05 1985-01-15 American Hoechst Corporation Polyester film coated with metal adhesion promoting copolyester
JPS61100490A (ja) * 1984-10-23 1986-05-19 Canon Inc 被記録材及びこれを用いたカラー画像の形成方法
US4956225A (en) * 1987-04-02 1990-09-11 Xerox Corporation Transparency with a polymeric substrate and toner receptive coating
US4952650A (en) * 1987-07-27 1990-08-28 Minnesota Mining And Manufacturing Company Suspension polymerization
GB8726661D0 (en) * 1987-11-13 1987-12-16 Shell Int Research Manufacture of synthetic saponites
US4869955A (en) * 1988-03-11 1989-09-26 E. I. Du Pont De Nemours And Company Polyester support for preparing electrostatic transparencies
US4912009A (en) * 1988-12-30 1990-03-27 Eastman Kodak Company Toner composition and method of making
GB8916030D0 (en) * 1989-07-13 1989-08-31 Ici Plc Imagable copy film
US5202205A (en) * 1990-06-27 1993-04-13 Xerox Corporation Transparencies comprising metal halide or urea antistatic layer
US5104731A (en) * 1990-08-24 1992-04-14 Arkwright Incorporated Dry toner imaging films possessing an anti-static matrix layer
US5167987A (en) * 1991-11-04 1992-12-01 Xerox Corporation Process for fabricating electrostatographic imaging members

Also Published As

Publication number Publication date
US5310591A (en) 1994-05-10
JPH06222603A (ja) 1994-08-12
CA2105909A1 (fr) 1994-03-19
AU669553B2 (en) 1996-06-13
KR940007614A (ko) 1994-04-27
DE69310653D1 (de) 1997-06-19
DE69310653T2 (de) 1998-01-02
AU4625893A (en) 1994-03-24
CA2105909C (fr) 2005-11-15
JP3469920B2 (ja) 2003-11-25
EP0588724A1 (fr) 1994-03-23
KR100276366B1 (ko) 2000-12-15

Similar Documents

Publication Publication Date Title
EP0588724B1 (fr) Feuille réceptrice d'images pour copieurs sur papier ordinaire
EP0588723B1 (fr) Support d'impression d'image transparent en solution aqueuse pour copieurs à papier ordinaire
EP0792479B1 (fr) Compositions de latex a noyau/coque a base d'eau, susceptibles de recevoir du toner
US5518809A (en) Water-based transparent image recording sheet for plain paper copiers
US5411787A (en) Water based transparent image recording sheet
EP0332183B1 (fr) Transparents électrostatiques contenant un support en polyester
US20030087991A1 (en) Water-based ink-receptive coating
JPH03136891A (ja) 非衝撃式印刷用レセプターとしての改良要素
EP0724518B1 (fr) Feuille support d'enregistrement d'images transparente et a base d'eau
US5319400A (en) Light-blocking transparency assembly
WO1999039914A1 (fr) Feuille pour encrage
WO1996016120A1 (fr) Feuille transparente a base d'eau pour l'mpression d'images, destinee a des photocopieurs a papier ordinaire
EP0695973A1 (fr) Film en couche mince détachable non poreux et opaque
JPH0619180A (ja) 電子写真用フィルム
JPH0619179A (ja) 電子写真用フィルム
JPH0764314A (ja) 電子写真用被転写フィルム及び加熱定着方法
JP3184064B2 (ja) 低剥離帯電性フイルム

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19940808

17Q First examination report despatched

Effective date: 19951106

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE FR GB IT LI NL SE

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69310653

Country of ref document: DE

Date of ref document: 19970619

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: E. BLUM & CO. PATENTANWAELTE

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20030909

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20030923

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050401

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20050401

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20050908

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20050919

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20050921

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20051031

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060917

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20060930

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070403

EUG Se: european patent has lapsed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20060916

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20070531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060916

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061002

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070916